CN110139756A - Reduce paint film applique, product and the method for defect - Google Patents

Abstract

The polymer film of in-situ polymerization helps to improve paint film applique, reduces defect.Paint film applique includes the polymer film and at least one nonferrous layer of the in-situ polymerization as carrier layer, the polymer film of in-situ polymerization and at least one described nonferrous layer are assembled into layered product, and the optionally described paint film applique further includes at least one top coat bed of material in a main surface of layered product and the adhesive phase in another main surface of layered product.

Description

Reduce paint film applique, product and the method for defect

Cross reference to related applications

This application claims on September 20th, 2016 it is submitting, application No. is 62/396,825 U.S. Provisional Patent Application and On March 11st, 2017 is submitting, application No. is the priority of the PCT Patent Application of PCT/US17/21982, by quoting two Person is fully incorporated herein.

Technical field

The present invention relates generally to reduce the paint film applique of defect, make and use the method for the paint film applique and comprising this The product of paint film applique.

Background technique

Painted surface is commonly used in many different types of applications.Painted surface can not only improve the aesthetic beauty on surface Can, but also the functional characteristic of underlying surface can be improved and help to protect the underlying surface.Application is to transport as a kind of In industry, China and foreign countries' painted surface is commonly exposed in various environment, and some of environment may be very harsh to surface.It is transporting In defeated industry, the example of the product with this painted surface includes providing the vehicles land, waterborne and air transport.This A little vehicles include aircraft and motor vehicles, such as car and truck.Paint on these surfaces can play protect underlying surface from It is damaged caused by as this exposure.However, Qi Benshen also must be it is durable, with bear to the anti-of this disruptive environmental Multiple exposure.

Many challenges are brought to the outer surface japanning of the vehicles, not only due to it is generally necessary to the surface area amount of japanning And the pattern that this surface is usually uneven, but also due to increasingly severe environmental legislation.For example, it is desired to and more and more Laws and regulations requirement reduce volatile organic component (VOC) discharge, especially utilizing a large amount of paint and other organic chemicals In industry.Therefore, VOC emission reduction relevant to conventional enamelling process and it is water-saving be more and more important environmental considerations.

With the relevant further consideration of outer surface japanning to the vehicles in the vehicles, especially carrier Factor is overall weight.It paints and exists on the surface, while the aesthetics and functional characteristic for increasing surface, also increase to apply and be somebody's turn to do The weight of the product of paint.In carrier, additional weight cause consume excess of fuel and limit related vehicle can The passengers quantity or quantity of goods safely and effectively transported.

In addition, unique consideration relevant to the japanning on aircraft and similar vehicle or otherwise covering outer surface Factor is the influence of any coating or covering of relatively high vehicle speed to vehicle surfaces and thereon.For example, Windage relevant to running at high speed may make this coating or covering be difficult to keep uniform and sufficiently be bonded in the vehicles On surface.Therefore, for applied to the coating developed in such as outer surface of the vehicles of continental rise running on expressway and Covering is typically not enough to bear and crosses air or in the relevant challenge situation of the fair speed of continental rise runway.

It gives the outer surfaces of means of transport japanning relevant many challenges to using conventional method to overcome, has developed perhaps More paint substitute technologies, allow to traditional paint and minimize or avoid using traditional paint.For example, by by plastics and face Material injects together, and a kind of commercial products allow automaker to remove completely enamelling process from auto production line.This product Including by Saudi Basic Industries Corporation (Saudi Basic Industries Corporation, SABIC) with trade name LEXAN The resin on surface that SLX is sold, being used to form tradition japanning.

It the use of other alternative solutions routinely painted include that will paint alternative membrane or thin slice (also referred to as applique) is adhered to traffic work On the surface formed on tool.For example, the 3M company of Paul, MN (St.Paul, MN) sells for certain The paint alternative membrane and adhesive tape of such application.A kind of such film -3M^TMPaint alternative membrane F577 (3M^TM Paint Replacement Film F577)-be described as having the polychloroethylene film of the textured appearance of black matte, be used for the vehicles window frame, Sash, window extension, main body and door pillar, instrument panel assembly and lid (metal or plastics).Film -3M as another kind^TM Paint alternative membrane FTA9055J (3M^TMPaint Replacement Film FTA9055J)-be described for around automobile side Glass provides shading appearance.This film is described as providing high glaze (90% reflectivity) appearance of black and is desirably integrated into traffic Outer clear dope in tool design.Referring to the U.S. Patent Publication of Publication No. 2007/0047099；Patent No. 5,965, 256 United States Patent (USP)；The United States Patent (USP) of Patent No. 6,475,616；And the United States Patent (USP) of Patent No. 7,141,303, institute There are these patents all to transfer 3M Innovative Properties Company.

It is known that there are also other paint substitute technologies.For example, the United States Patent (USP) of Patent No. 5,034,275 is related to painting coated sheet Material.The material is it is said that include flexible and stretchable thermoplastic polyester carrier film, stretchable aqueous polyurethane paint layer, stretchable The transparent cross-linked polyurethane top coat bed of material and the thin articulamentum that is arranged between carrier film and paint layer, the articulamentum is by carrying The aqueous dispersion of the neutral copolymer of coating ethylene and ethylene formula unsaturated carboxylic acid on body film and formed.

The United States Patent (USP) of Patent No. 5,114,789 describes a kind of decorative sheets of material with transparent top coat material, the top Coating can be adhered in various substrates, such as automobile outer panels, as protectiveness and decorative coating.The sheet material includes thin load The top coat bed of material of body film, the paint layer being adhered on a surface of carrier film and crosslinking.In the embodiment wherein described, the top Dope layer is it is said that-at least 0.1 millimeter (100 microns) of " extremely thick ".

The United States Patent (USP) of Patent No. 5,242,751 describes a kind of composite paint product comprising the carrier of heat deformable Film, the carrier film have paint layer with adhesive phase and in its second main surface in its first main surface, the paint layer by The colored base composition covered by the polyurethane top coat bed of material.

The United States Patent (USP) of Patent No. 5,268,215 describes it is said that the paint coating film with good invulnerability.Polyurethane Paint layer is coated on polymer support film.Polyurethane clearcoat layer is coated on the upper surface of paint layer, is then coated with polyurethane- The siloxanes top coat bed of material.It is said that the film can with thermoforming, stretch and be adhesively adhered to automobile body components, ship, household electrical appliance In other substrates, as with primer-clear dope appearance protectiveness and decorative covering.

The United States Patent (USP) of Patent No. 5,468,532 describes a kind of multi-layer graphical product with nonferrous layer.It is based on Polymer film, the polymer film cover protective superficial layer, it is said that can make the product weatherable and chemicals-resistant exposure.It should Protectiveness superficial layer is described as polyurethane-based material in the exemplary embodiment.

The United States Patent (USP) of Patent No. 6,132,864 is described coated with two or more certain material coatings through applying The plastic foil of paint.The plastic foil is made of plastic-based film, and plastic-based film is initially coated with filler composition, is then applied with colored paint It covers, is then coated with overlay.The plastic-based film can be polyolefin, polyamide, polyurethane, polyester, polyacrylate, The mixture of polycarbonate or different polymeric materials.The filler composition is described as in addition to other groups exceptionally, containing adhesive With the composition of crosslinking agent.Colored paint coating is comprising polymer adhesive, is with or without crosslinking agent and pigment or pigment mixture Top coat material.It is identical that overlay is described as one of material and the material that is suitable as basement membrane.It is said that more described in it Layer thin slice has good anti-aggregate chips and corrosion resistance.

Although there are many substitute technology is painted, traditional technology is not satisfactorily addressed under all situations, especially relates to And the paint substitution in the application of the vehicles used in transport.Not only there is be commonly exposed to high wind due to this vehicles Enough bondings of its outer surface and the problem of durability caused by resistance, but also there is other problems.

As an example, many means of transports are increasingly dependent on what composite material was bonded in tradition paint alternative materials Application on surface.However, tradition paint alternative materials will not usually be adhered on independent material as it and be adhered to composite wood On material.Needed for known conventional paint alternative materials are sufficiently adhered to all surface (including the surface formed as composite material) and provide Aesthetics and the ability of functional characteristic are usually insufficient.It is not intended merely to material to be sufficiently adhered on surface, and also wants to needing It can be removed easily when wanting and change material.For example, logo and design often change, this is resulted in the need for aobvious for aircraft Show that the aircraft of out-of-date mark and design is renovated.This is especially universal in the case where leasing aircraft, and lease aircraft is often subjected to It is repetitious to occupy change, and therefore undergo relevant individual or company's mark and design alteration.In general, on renovation surface Shi Bixu removes the paint alternative membrane deposited on the surface first.However, many conventional films can not remove easily, because wherein Layer be easily delaminated.When getting on paint removal alternative membrane from surface, the layering for painting alternative membrane may be such that refurbishment process significantly complicates.

Even if refurbishment process is also likely to be present problem when there is paint on the surface wait renovate rather than paint alternative membrane.? When preparation coats new paint coating on the surface, renovation painted surface usually requires to polish to the surface.Because most of Chemical strippers cannot be used for composite material, so composite material surface usually has to rely on polishing to remove it in renovation Undesired paint above.However, polishing is also undesirable by the surface that composite material is formed, because this polishing may cause Damage (for example, rupture) (especially when the reinforcing material includes fiber) to the reinforcing material in composite material.

As another example, the basement membrane/carrier of multilayer film product (such as paint substitution applique) is conventionally used to due to being formed The preparation method that film generallys use is usually directed to the method for squeezing out and being used to form film by aggregated component with other, these films Chemical and physical features be restricted.The United States Patent (USP) of Patent No. 8,828,303 describes one in these limitations A bit.For example, some polymer chemistries due to the presence of its relatively high molecular weight and/or crosslinking without can be carried out hot melt plus Work, if not it is not possible that, the presence of relatively high molecular weight and/or crosslinking all makes it difficult to lower than polymer composition Or hot melt processing is carried out to the prefabricated pellet of composition under the degradation temperature of formation substrate with the membrane thereon and (is gathered generally according to being formed The conventional method of compound film is carried out using hot melt processing).

Wet cast polymer film forming method also has its disadvantage.No matter the system is solvent type or aqueous, first must It must be coated in required substrate, then drying to remove solvation medium or decentralized medium (is respectively organic solvent Or water), to form polymer film.Therefore, it may be problematic for the polymer film of adequate thickness being formed using wet casting method. In addition, since these polymer or its ingredient lack enough solubilities in Conventional solvents and decentralized medium, these polymer Chemical substance cannot use wet casting method to form polymer film.

Therefore, the characteristic of conventionally fabricated polymer film is formed the specific polymer of those of film by usable conventional method Chemical substance is limited, furthermore, which is usually directed to the other sides for squeezing out and being formed for the composition by having polymerize film Method.Due to the forming method of conventionally fabricated polymer film and method that they are in turn laminated to adjacent membranes, this is conventionally fabricated Polymer film is commonly subjected to the defect as caused by least one of gelation, die head line and gage line.Since defect is to finished product Such as the negative effect of visual characteristic, the generality of defect to need that the polymer film of formation is tested and divided in detail Analysis, to ensure that the polymer film is suitable for intended application.

Gelation leads in finished product that there are gel particle (also referred to as " gels ")." gel " is generally understood as sticky group Object is closed, can be for example, at least partially polymerized composition, the composition with relatively high molecular weight in Polymer Processing And/or the composition containing a large amount of gas-entrained (for example, air or byproducts of reaction, such as carbon dioxide).Gel can be with each Kind of form its own is presented and polymer film is usually processed by the composition polymerizeing during it is excessively thermally-induced.For example, gel Cross-linked form can be taken, by the delay of resin in extrusion process and/or dead zone catalyst or other organic or inorganics it is residual Object is stayed to cause, the appearance (for example, the carbon dioxide bubble generated by moisture) by aoxidizing relevant degradation causes or root is in confession Answer chain.Gelation, which may make, is difficult to be formed uniform polymer material layer (for example, film).

Other than forming polymer film, in order to provide appearance coloured or beautiful needed for being used as paint film applique, usually The more than one polymer film and more than one polymer film is laminated together is provided, wherein at least one polymer film is Coloured.However, due to the laminar manner of polymer film, often will appear defect when polymer film is laminated together.Often Rule ground, usually utilizes heat to polymer film is laminated together.It is well known, however, that heat lamination can generate various defects.Specially Benefit number describes the problem related to defect caused by heat lamination for 5,641,374 United States Patent (USP).Those defects include for example Gauffer, ripple, curling, excess shrinkage or stretching, wave, walf checks (waffle), color density loss and microvesicle.

Source regardless of defect, they all may cause aesthstic flaw in polymer film and paint film applique, weakness Point and rupture, and their applicabilities in numerous applications would generally be damaged.Therefore, in entire supply chain exhaustive effort with Determine the presence and degree of defect.When being visually observed with the mankind, many defects can be easily detected.Also other inspections can be used The method for surveying defect, including spectroscopy.When a defect is detected, it is often necessary to it is discarded to contain defective polymer film, cause phase When big waste.

As described above, pass conventional paint substitute technology fail sufficiently to solve the problems, such as it is many.Therefore, there is still a need for alternative Paint substitute technology.

Summary of the invention

Need for alternative polymer film of related paint film applique and product with and forming method thereof, for it Assign improved characteristic.According to the present invention, the polymer film of in-situ polymerization is conducive to improve paint film applique.It is preferred that flawless poly- Compound film and paint film applique, flawless thin polymer film is a part of paint film applique, therefore the defect of paint film applique also subtracts It is few.

In one embodiment, paint film applique includes the flawless polymer film as carrier layer.With include conventional shape At Polyurethane carrier layer (that is, the routine, which forms to be usually directed to, squeezes out and is formed by aggregated composition other sides of film Method, wherein be used to form the material of film be aggregated in be formed before film by it be basically completed) conventional multilayer thin slice compare, this hair Bright paint film applique independent of such layer as carrier layer, the result is that also improving other than the treatment effeciency thus assigned Characteristics needed for one or more.

Application No. is PCT/US17/21982, entitled " Defect-Free Polymer Films and Related The co-pending PCT Patent Application of Protective Sheets, Articles, and Methods ", which describe, can be used as this The zero defect polymer film of carrier layer in invention paint film applique, this application are incorporated herein by reference in their entirety.According to the present invention One aspect, when assembling paint film applique, the zero defect polymer film for forming carrier layer gathers in situ on adjacent nonferrous layer It closes.

It should be appreciated that it is as used herein, when polymerisable compound " original position " aggregates into required polymer film, comprising being somebody's turn to do The polymerization of the polymer of film starts prior to, concurrently with, or after polymerisable compound is positioned to required form membrane soon just, And soon in this position fixing process or later, polymerization reaction is basically completed.In general, making when referring to the time that polymerization starts " existing just ... before " and refer to no more than about 30 seconds periods " soon later ".Surprisingly, it has been found that removing Thus it except the treatment effeciency assigned, is additionally aided needed for improving using the carrier layer of the in-situ polymerization on adjacent nonferrous layer Paint film applique characteristic.

Detailed description of the invention

Fig. 1 is compared with those of the Polyurethane carrier layer correlation routinely formed characteristic, for paint film applique of the invention In-situ polymerization Polyurethane carrier layer fissipation factor (also referred to as Tan δ) and temperature relational graph.

Fig. 2 is compared with those of the Polyurethane carrier layer correlation routinely formed characteristic, for paint film applique of the invention In-situ polymerization Polyurethane carrier layer storage modulus and temperature relational graph.

Specific embodiment

Phrase " paint film applique " covers film, which consists essentially of the uniform film of color on the whole and such film: should Film itself combines the color change including figure, pattern and other non-homogeneous dispersions on the whole with other paint alternative membranes.This hair Bright paint film applique generally includes the polymeric layer and nonferrous layer of in-situ polymerization.In a further embodiment, paint film applique packet Adhesive phase is included, described adhesive layer, which has, is disposed therein and/or is arranged in the nonferrous layer on the outer surface of polymeric layer.Have Chromatograph includes at least one colour induction component, and uniformly or non-uniformly color is provided in entire film.When colour induction group When point being pigment, " coloring layer " is also referred to as nonferrous layer mentioned by exemplary embodiment of the present invention is being described herein.

Advantageously, paint film applique of the invention can not only cover surface with improved characteristic, but also can be than including The conventional paint film applique of the carrier layer routinely formed removes cleaner.It has been found that adjacent with nonferrous layer excellent by providing Select flawless polymer film as carrier layer, so that removing remaining adhesive residue on the surface of paint film applique after use Minimum or elimination, compared to energy relevant to the carrier layer routinely formed and/or impact, which can inhale during stretching Receive more energy and/or impact.That is, compared with the relevant damping characteristic of the carrier layer routinely formed, it is of the invention Improved carrier layer used in paint film applique can show more effective damping characteristic (" peak loss as described herein The factor " is proved).In layered product include this layer adjacent with nonferrous layer be conducive to during paint film decal application carrier layer and Preferably continue to bond between nonferrous layer, therefore, a possibility that interlaminar delamination, is lower, and after removing paint film applique from surface, Residual adhesive and other materials on surface is less.

According to another aspect of the present invention, when using this carrier layer, according to the present invention, paint film applique is better balanced The characteristic of interior individual layer.For example, when in paint film applique, such as in multistage paint (for example, with conventional base coating/transparent The appearance of coating lacquer painting) in, when there is the top coat bed of material of opposite high-modulus, the adjacent carrier layer of this top coat bed of material has opposite High fissipation factor is convenient for that paint film applique is made to stretch and/or impact on Shi Qi thickness the rate and recovery journey that have more evenly Degree.

Although the presence of the top coat bed of material be it is non-essential, it can reside in multistage paint for example according to the present invention, The multistage enamel-cover includes combination of the carrier layer (or multiple carrier layers, if necessary) at least one nonferrous layer, and the combination is in side Flank at least one adhesive phase (i.e. the combination of aforementioned layers is similar to the primer in conventional paint system), the other side flank to Few top coat bed of material (that is, being similar to the clear dope in conventional paint system).

It should be understood that series relevant to paint is usually corresponding with the top coat bed of material number in paint film applique.For example, according to this hair In one embodiment of bright two-stage paint, paint film applique with lower layer substantially by being formed: adhesive phase, carrier layer, nonferrous layer and The top coat bed of material, carrier layer and nonferrous layer are located in any order between adhesive phase and the top coat bed of material.According to the present invention two In another embodiment of grade paint, paint film applique with lower layer substantially by being formed: adhesive phase, carrier layer, two different have Chromatograph and the top coat bed of material, carrier layer and two different nonferrous layers are located in any order between adhesive phase and the top coat bed of material. Exemplary three-level paint according to the present invention may include any one of aforementioned two-stage paint and adjacent with the first top coat bed of material another The outer top coat bed of material.

Preferably, paint film applique of the invention advantageously can not only be with the characteristic covering surface that more balances and from table Leave less residual adhesive after the removal of face, and they also there is the restorability of enhancing with realize enough coverings and It is readily applied to non-planar surfaces.As used herein, " restorability " refers to that material is stretched and substantially restores after the stretch To the ability of its reset condition.Preferred paint film applique is when stretching (extending) reaches its about 125% initial length to length It can essentially return to its reset condition.Preferably, paint film applique is when being stretched to length up to its about 150% initial length It can essentially return to its reset condition.According to an aspect of the present invention, paint film applique can extend before breaking to Length, which reaches, is greater than its about 200% initial length.

An exemplary embodiment of the present invention, due to its forming method, paint film applique advantageously comprises flawless poly- Compound film is as the carrier layer adjacent with nonferrous layer.In another embodiment, have zero defect polymer film as carrier layer Paint film applique further include at least one of the top coat bed of material and adhesive phase.

One aspect according to further embodiments, paint film applique include following successive layer: as the intact of carrier layer Fall into polymer film；Nonferrous layer；And adhesive phase.According to the other side of the further embodiment, paint film applique includes such as Under successive layer: nonferrous layer；Zero defect polymer film as carrier layer；And adhesive phase.According to the further embodiment Another aspect, paint film applique includes following successive layer: the top coat bed of material；Zero defect polymer film as carrier layer；With And nonferrous layer.According to the other side of the further embodiment, paint film applique includes following successive layer: the top coat bed of material；Have Chromatograph；And the zero defect polymer film as carrier layer.

Further embodiment in terms of latter two successively includes adhesive phase, so that the adjacent nonferrous layer of adhesive phase or carrier Layer exposure outward.Exemplary paint film applique includes following successive layer: the top coat bed of material；Zero defect polymer as carrier layer Film；Nonferrous layer；And adhesive phase.Another exemplary paint film applique includes following successive layer: the top coat bed of material；Nonferrous layer；Make For the zero defect polymer film of carrier layer；And adhesive phase.

For the ease of processing weight and cost and make weight and cost minimization, it is preferable that the overall thickness of paint film applique is small In about 130 microns.In one embodiment, the overall thickness of paint film applique is about 100 microns to about 130 microns thickness.At another In embodiment, the overall thickness of paint film applique is about 50 microns to about 75 microns thickness.It is detailed further below in paint film applique Each of individually and isolated layer.

Carrier layer

By using " carrier layer " of this paper, it should be understood that the polymer film including the carrier layer is at least held in paint film applique Carry (that is, support) adhesive phase and different nonferrous layers.Although the thickness of nonferrous layer and/or adhesive phase can be greater than carrier layer Thickness, still, carrier layer is to provide the fundamental of the paint film applique with required characteristic, and no matter these characteristics are aesthetics , it is functional or other.

When assembling paint film applique of the invention, carrier layer in-situ polymerization on adjacent nonferrous layer.It is according to the present invention The zero defect polymer film of preferred embodiment, at least one other layer of support is used as carrier layer.In some cases, carrier layer It is referred to as " basal layer ", " supporting layer " or similar title.In general, the carrier layer of paint film applique of the invention includes at it It is known as " middle layer " when multiple layers (i.e. quantity be " n " individual course).However, according to other embodiments of the invention, the present invention The carrier layer of paint film applique can be single film layer.When multiple layers of formation carrier layer, each of " n " a individual course can To be identical or different chemical substance.In one exemplary embodiment, each of " n " a individual course has basic phase Same chemical substance.

According to application, the carrier layer can be transparent or coloring.When carrier layer is transparent, nonferrous layer is usual It is arranged between carrier layer and adhesive phase.When carrier layer be it is transparent when, nonferrous layer alternatively or with another nonferrous layer In conjunction on the outer surface that carrier layer is arranged in.When carrier layer is coloring, nonferrous layer is generally arranged at the outer surface of carrier layer. In this embodiment, carrier layer can use material (for example, titanium dioxide) dipping for making carrier layer serve as reflecting background, when will paint The nonferrous layer covered is set to show color when in film decal application to surface.

It according to a preferred aspect of the present invention, is based on polyurethane for the carrier layer of paint film applique of the invention. For the sake of simplicity, the term as used herein " polyurethane " includes containing urethane (also referred to as carbamate) key, urea bond or its group Close the polymer of (that is, in the case where poly- (urethane-urea)).Therefore, polyurethane carrier layer include at least urethane bond, urea bond or A combination thereof.In addition, polyurethane carrier layer is based on such polymer: wherein main polymer chain has former in the course of the polymerization process At least the 40%, preferably at least 60% of position formation, more preferably at least 80% urethane and/or duplicate urea bond.

Polyurethane carrier layer is prepared by making component reaction according to the method for the present invention, the component includes at least one Kind of isocyanate-reactive (for example, hydroxy-functional, such as polyalcohol) component and at least one isocyanate-functional (for example, polyisocyanates) component.For example, Patent No. 8,828,303, entitled " Methods for Polymerizing Describing in the United States Patent (USP) of Films In-SituUsing a Radiation Source " can be used for side according to the present invention Method forms the component of the exemplary polymerisable compound of polyurethane carrier layer, which is incorporated herein by reference of text.? In preferred embodiment, the polymerisable compound of this aspect according to the present invention includes aliphatic component, more preferably substantially by Aliphatic component composition.

In the exemplary embodiment, using selected from the radiation of at least one of ultraviolet radioactive, heat radiation and electron beam irradiation The polymerization of polymerisable compound is caused in source.Continuous processing or batch processing can be used in method of the invention.For example, in this hair In bright one embodiment, relatively low energy ultraviolet radiation can be used and (be less than about 100mW/cm for example, having²Energy Amount) carry out the continuous processing of polyurethane carrier layer, such as the in-situ polymerization based on net.As another example, in the present invention Another embodiment in, batch processing can be used, such as ultraviolet solidifiable composition is coated to the substrate of separation It goes up and irradiates the substrate so that polyurethane carrier layer is formed in situ.

A preferred aspect according to the method for the present invention, is used to form the polymerisable compound of carrier layer substantially free of molten Agent.However, different from the hot melt system substantially free of solvent, the polymerisable compound of preferred aspect is being applied according to the present invention To being liquid at room temperature when polymerization has in the substrate of the polymerisable compound above.In addition to relevant to solvent-based processing Such as except environmental and safety problems, solvent-based processing usually requires to carry out the effectively group from polymerization using raised temperature It closes in object and removes excessive solvent.It is therefore preferable that carrier layer is substantially free of unreacted solvent.Correspondingly, it is preferably formed as carrying The polymerisable compound of body layer is substantially free of solvent.According to these preferred embodiments, sustainable paint technology is promoted.

Any suitable additive may be present in carrier layer.Those skilled in the art is selected based on expected application Other known additives of member.Those skilled in the art can determine the amount of these additives for required effect easily.When Carrier layer be coloring when, it has therefore been surprisingly found that assign pigment loading that the identical color of carrier layer needs than needing The amount for being added to the pigment in the polymer film routinely formed for serving as carrier layer is low.Therefore, according to the present invention, due to adding face Any adverse effect expected and generated to the ductility of carrier layer or other properties is all minimized.One according to the present invention Aspect, it is elastic that those of ordinary skill in the art, which understand resulting carrier layer substantially,.In order to by a variety of reactive components It obtains these benefits in the polyurethane of polymerization or other similar polymer films, color is preferably added to the more of mixing and reaction In at least two components in kind component.Therefore, benefit is obtained on treatment effeciency.

According to one embodiment of present invention, carrier layer with a thickness of about 5 microns to about 1,250 micron.According to further Embodiment, carrier layer with a thickness of about 8 microns to about 260 microns.Wherein quantity is each film in the individual film layer of " n " Layer can be as thin as about 5 microns and thickness of about 50 microns, the presence of thicker layer is used in particular for such as trajectory application.However, In order to assign bigger restorability, according to an aspect of the present invention, using with a thickness of about 220 microns or smaller carrier Layer.According to further aspect, carrier layer with a thickness of about 180 microns or smaller.For example, the thickness of carrier layer can be about 120 microns to about 180 microns.The restorability of carrier layer is not only increased by using relatively thin carrier layer, and is thus enhanced The restorability of entire paint film applique, this mode reduce the totle drilling cost of paint film applique.

With the carrier layer including routinely being formed (that is, routine formation is usually directed to extrusion and by aggregated composition Formed film other methods, wherein be used to form the material of film be aggregated in by the material is formed film before be basically completed) it is normal Rule paint film applique compare, paint film applique of the invention independent of such layer as carrier layer, the result is that in addition to thus assigning Treatment effeciency except it was also surprisingly that improve it is one or more needed for characteristics.For example, the size with extruded film can be made Problem described in the problem-of the unstability correlation such as United States Patent (USP) of Patent No. 5,985,079 minimizes.

According to an aspect of the present invention, the improved polyurethane carrier layer in paint film applique of the invention is in situ poly- It closes.For example, the United States Patent (USP) of Patent No. 8,828,303 and the United States Patent (USP) of Publication No. US-2011-0137006-A1 are public It opens and describes the method formed by this in-situ polymerization and film, this two documents are both incorporated herein by reference.It is wondrous , using the carrier layer of in-situ polymerization other than the treatment effeciency thus assigned, physics needed for also promoting improvement is special for discovery Property.

Different from common extrusion type routine carrier layer, the carrier layer of in-situ polymerization of the invention is substantially generally not heat Plasticity.However, the carrier layer of in-situ polymerization of the invention seems and makes one to feel non-with traditional extrusion type carrier layer It is often similar.However, improved polymer architecture provides some dramatically different spies for the carrier layer of in-situ polymerization of the invention Property, including dimensional stability.

Another dramatically different characteristic is solvent resistance.The solvent resistance of the carrier layer of currently preferred in-situ polymerization Close to solvent resistance relevant to conventional crosslinking (i.e. thermosetting property) material.Thermoplastic material is typically, extrusion type material Generally be completely dissolved when being impregnated in solvent (such as tetrahydrofuran), and in-situ polymerization material of the invention be impregnated in it is identical It only shows slightly to be swollen when solvent.

Another dramatically different characteristic is storage modulus.Thermoplastic material is typically, extrusion type material is general It shows as storage modulus and continuously declines as temperature increases.However, the energy storage of the carrier layer of currently preferred in-situ polymerization Modulus is dramatically different, because it shows rubber-like platform area, this is and the consistent feature of lightly crosslinked elastomer.At one In embodiment, the storage modulus of the polyurethane carrier layer of preferred in-situ polymerization is than the thermoplastic poly ammonia under conventional extrusion temperature High about two orders of magnitude of the storage modulus of ester.

According to another aspect of the present invention, it is carried out when according to fissipation factor test method described below as independent film When test, the peak loss factor of the improved polyurethane carrier layer in paint film applique of the invention is at least about 0.5, at least About 0.8, or even at least about 1.2.

As shown in Figure 1, poly- according to the extrusion type (routinely being formed) that fissipation factor test method described below measures Urethane carrier tunic the peak loss factor (that is, as labeled as A, B and C data and curves shown in, A, B and C indicate from Argotec, LLC (Greenfield, Massachusetts (Greenfield, MA)) are obtained through commercial channels, product name The extrusion type polyurethane base carrier layer of respectively ARGOTEC 49510, ARGOTEC 49510-60DV and ARGOTEC 46510) The peak loss factor of Polyurethane carrier layer substantially less than according to the present invention, the peak value of Polyurethane carrier layer according to the present invention Fissipation factor is greater than 0.5 (i.e. as shown in the data and curves labeled as 1 and 2).Also as shown in Figure 1, to extrusion type polyurethane carrier The peak loss factor that film measures occurs at about 25 DEG C, and to the polyurethane basement membrane for being used as carrier layer in paint film applique of the invention The peak loss factor measured about occurs at least about 35 DEG C of temperature.

In addition, the half high fissipation factor measured to the polyurethane basement membrane for being used as carrier layer in paint film applique of the invention (should Fissipation factor is the half of peak loss factor values, and there are two every curves) (it is lower than in some embodiments below about 40 DEG C About 30 DEG C, in addition in some embodiments be below about 20 DEG C) temperature span in occur, on the contrary, extrusion type polyurethane base polymerize The high fissipation factor of the half of object film goes out in the temperature span of greater than about 40 DEG C (or even being greater than about 45 DEG C in the exemplary embodiment) It is existing.It is the data and curves with B for label in Fig. 1, half high fissipation factor is measured at 53 DEG C.For marking the number for being in Fig. 1 According to curve, half high fissipation factor is measured at 49 DEG C.For marking the data and curves for being in Fig. 1, measured at 18 DEG C half high loss because Son.For marking the data and curves for being in Fig. 1, half high fissipation factor is measured at 22 DEG C.

As shown in Fig. 2, according to storage modulu test method described below, compared to as in paint film applique of the invention The polyurethane based-polymer film of carrier layer, extrusion type (routinely form) storage modulu that polyurethane film measures (that is, as marked Shown in data and curves for A, B and C) under relatively lower temp it is reduced to particular value.

It is preferred that the carrier layer in paint applique of the invention is flawless.As used herein, " defect " It is interpreted as vision and lacks flaw, such as gel particle, die head line or gage line.As used herein, " zero defect " refers to have and not surpass The polymer film that maximum shown in table 1 allows defect is crossed, as described according to greatest drawback diameter.

Table 1

Preferably, when being visually observed by people, the defect that not can be detected in polymer film.It is highly preferred that working as When being observed with being up to about the amplification factor of 50x, without detectable defect in polymer film.

Advantageously, in a preferred embodiment, due to not forming the polymer film as carrier layer in conventional reactor, So conventional p- gel cannot be formed.Equally, in a preferred embodiment, it will form polymerization due to using conventional extruders not Object film, so conventional e- gel cannot be formed.Once polymerization, as the preferred of the carrier layer in paint film applique of the invention Polymer film never lives through pyroplastic deformation, from without extruder, and never under conventional extrusion temperature, experience is overheated Drift.In addition, in view of preferred thin polymer film being formed using conventional extruders, processing aid-for example lubricates and prevents Adhesion additive-is known to be contributed to form gel and is conventional needs, and when assembling paint film applique according to the present invention, at this It does not need in kind forming method using the processing aid, and preferably excludes the processing aid from the method for forming polymer film. Obtained polymer film is flawless, and polymer film is reduced as the defect of the paint film applique of a part therein.

Nonferrous layer

Although for simplicity can only be tied in paint film applique of the invention using more than one nonferrous layer The such layer of unification is described below.If should be understood that each nonferrous layer can be identical using multiple nonferrous layers Or it is different.

Nonferrous layer includes any suitable material, and when by paint film decal application to surface, and nonferrous layer provides institute The aesthetic feeling needed.Nonferrous layer can be continuous or discontinuous layer.Note that nonferrous layer can be substantially made of figure, pattern etc., This makes the layer be discontinuity layer and/or non planar layer.

Nonferrous layer includes at least one colour induction component.In the broadest sense, colour induction component includes only The component of the opacity of nonferrous layer is influenced, the component of the spectral color of nonferrous layer is only influenced, and only influences the color of nonferrous layer The component of color, coloration or tone.In the case where those components influence opacities, opaque nonferrous layer can get, therefore It can get opaque paint film applique.In the case where components influence color, coloration or tone, it is understood that color be color with it is white The mixing of color, white increase brightness.Coloration is the mixing of color and black, and black reduces brightness.Tone by color with The mixing of grey, or generated by dyeing and gradual change.Color is mixed with any muted color (including black, grey and white) Chroma or coloration are reduced, while form and aspect remain unchanged.

Colour induction component for use in the present invention includes, for example, those of ordinary skill in the art be commonly referred to as pigment, The component of paint, coloring agent, sheet metal and dyestuff.Pigment is exemplary colour induction component.In the exemplary embodiment, have Chromatograph includes ink.Any suitable commercially available ink can be used.The non-limitative example of suitable ink includes the propylene of coloring Sour ink (the quick-drying acrylic ink including coloring), urethane ink, epoxy ink and the urethane enamel paint coloured, such as by The PRC Desoto International of California Glenn Dai Er (Glendale, CA), Inc. is with trade name The coating that DESOTHANE HS is sold.

Any suitable additive can be optionally included in nonferrous layer.For example, stabilizer is (for example, antioxidant, heat Stabilizer and UV stabilizer), crosslinking agent (such as aluminium or melamine crosslinkers), corrosion inhibitor, plasticizer, photocrosslinking agent, Other colorant, filler and other conventional additives well known by persons skilled in the art can be incorporated into nonferrous layer.If It needs, adhesion promotor may be embodied in nonferrous layer.However, in a preferred embodiment, selection includes the material of nonferrous layer With with adjacent layer (including carrier layer) chemical compatibility in paint film applique.Further, since carrier layer is former on adjacent nonferrous layer The fact that position polymerization, the adhesion between layer is enhanced.Although be not intended to it is bound by theory, it is believed that in carrier layer and thereon In-situ polymerization, which has, generates interlayer entanglement or crosslinking between the nonferrous layer of carrier layer.Therefore, preferred embodiment in accordance with the present invention, no Need adhesion promotor.

Preferably, nonferrous layer substantially free of the outer surface that may tend to move to paint film applique or in which interface Component, wherein these components can promote interlaminar delamination or otherwise negatively affect in paint film applique with adjacent surface or The bonding of layer.Nonferrous layer is preferably resistant to the chemicals that nonferrous layer may expose during paint film applique use.For example, it is preferable to Ground, nonferrous layer is water-fast, and (for example, by the TBM of St. Louis (St.Louis, MO), Inc. is with commodity with hydraulic fluid Name SKYDROL sell hydraulic fluid) degradation, especially nonferrous layer includes paint film after in paint film decal application to surface When the outer layer of applique.

Nonferrous layer can be formed according to any suitable method.In one embodiment, nonferrous layer is by the composition that polymerize It is formed with solution-cast.For example, nonferrous layer can be cast by organic solvent solution.As another example, nonferrous layer can To be cast by aqueous solution.

In yet another embodiment, nonferrous layer is in-situ polymerization.As described above, the U.S. of Patent No. 8,828,303 Patent and the U.S. Patent Publication of Publication No. US-2011-0137006-A1 describe the side formed by this in-situ polymerization Method and film.One preferred aspect of the embodiment is nonferrous layer by solvent-free polymerisable compound (at room temperature in pure shape The liquid of formula) in polymerization (on-web polymerization) on the net.

In a preferred embodiment, nonferrous layer is reactive polymer film." reactivity " is interpreted as polymer film Chemical functional enables interface of the carrier layer polymerizeing on it between two adjacent layers and nonferrous layer to be formed covalently Key.According to this embodiment on one side, reactive polymer film include can with formed carrier layer polymerisable compound in Such as isocyanate functional group reaction hydroxy functional group.

Nonferrous layer includes any suitable thickness.According to one embodiment of present invention, nonferrous layer with a thickness of about 5 microns To about 1,250 microns.According to further embodiments, nonferrous layer with a thickness of about 8 microns to about 260 microns.In another implementation Example in, nonferrous layer with a thickness of about 12 microns to about 125 microns.In yet a further embodiment, nonferrous layer with a thickness of About 25 microns to about 75 microns.In another further embodiment, nonferrous layer with a thickness of about 8 microns to about 25 microns.Example Such as, as long as when by paint film decal application to surface, the color of paint film applique is enough from outside as it can be seen that the thickness of nonferrous layer It can be with significant changes without departing from the spirit and scope of the present invention.Although enhancing entire paint film by using relatively thin nonferrous layer The flexibility of applique, but the totle drilling cost of paint film applique can also be reduced in this way.

Non-essential adhesive phase

When there are adhesive phase, adhesive phase is positioned to adjacent with layered product and is located on the principal plane side of layered product, With there are the principal plane side of any non-essential top coat bed of material is opposite, the layered product includes at least one carrier layer and at least one A nonferrous layer.Any suitable adhesive can be used for adhesive phase according to the present invention.In a preferred embodiment, adhesive phase Include contact adhesive.

Although any suitable chemical substance can be used for the base polymer in adhesive phase, preferred (methyl) acrylic acid Ester-i.e. acrylate and methacrylate-chemical substance.However, other suitable chemicals as known to those skilled in the art Matter, including for example based on synthesis and natural rubber, polybutadiene and its copolymer, polyisoprene and its copolymer and siloxanes The chemical substance of (such as dimethyl silicone polymer and polymethylphenylsiloxane).Any suitable additive can be with adhesive phase In base polymer exist jointly.

Particularly, 2- ethylhexyl acrylate, vinyl acetate and acrylic acid well known by persons skilled in the art are based on The adhesive of monomer polymerization is found in one embodiment for use in the present invention.Adhesive can be crosslinked, for example, using conventional Aluminium or melamine crosslinkers.

In one embodiment, adhesive phase with a thickness of about 5 microns to about 150 microns.In a further implementation Example in, adhesive phase with a thickness of about 10 microns to about 100 microns.In another further embodiment, adhesive phase With a thickness of about 30 microns to about 100 microns.However, without departing from the spirit and scope of the present invention, adhesive phase Thickness can be with significant changes.

Before adhesive phase is applied on surface, for example conventional release lining can be used to protect adhesive Layer.In this way, thin slice may be easy to volume or other forms storage and transport until its application.

The non-essential top coat bed of material

In general, it is opposite with any adhesive phase in paint film applique of the invention, in carrier layer and coloured layer laminate Dominant plane side on any exposed non-adhesive layers outward be referred to as " the top coat bed of material ".It is consistent with its title, when will paint When in film decal application to product, the inessential existing top coat bed of material is outer layer exposed outward in paint film applique.It is any suitable Material type paint film applique for use in the present invention in the top coat bed of material.For example, the top coat bed of material polymerize based on may include Polycarbonate, polyvinyl fluoride, poly- (methyl) acrylate (for example, polyacrylate or polymethacrylates), poly- ammonia of object Ester, its modification (for example, hydridization) polymer or combinations thereof.United States Patent (USP) referring to Patent No. 4,476,293 is to can be used for this The description of the exemplary polycarbonate-based polyurethane of the invention top coat bed of material.See also Publication No. US-2008-0286576-A1's Description of the U.S. Patent Publication to the other exemplary top coat bed of material, the patent disclosure are incorporated herein by reference.

In one embodiment, after paint film applique is adhered to underlying surface, using (for example, logical on paint film applique Cross and spray the top coat bed of material or with the japanning of the top coat bed of material) the top coat bed of material.Preferably, in this embodiment, make using the top coat bed of material Proper applique is adhered on surface in use, being exposed in environment without paint film applique.In addition, when more than one paint film pastes When colored and other combinations are on surface, the top coat bed of material preferably covers and protects the seam between adjacent paint film applique from exposure In environment.

In another embodiment, the top coat bed of material is included in one of the layer in paint film applique.For example, according to the present invention Multistage enamel-cover includes combination of the carrier layer (or multiple carrier layers, if necessary) at least one nonferrous layer, and the combination is in side side At least one adhesive phase (i.e. the combination of aforementioned layers is similar to the primer in conventional paint system) is connect, and is flanked in the other side At least one top coat bed of material (that is, being similar to the clear dope in conventional paint system).The two-stage paint of property embodiment according to the example With a top coat bed of material.There are two the adjacent but different top coat bed of materials for the three-level paint tool of property embodiment according to the example.

The top coat bed of material may include any suitable chemical substance.In general, the top coat bed of material provides one or more characteristics, it is described One or more characteristics include the following: environmental resistance, chemical resistance, wearability, scratch resistance, optical transparence and it is other usually Required characteristic.Although the carrier layer or coloured exposed outward in any other manner when by paint film decal application to product Layer can provide required characteristic, so that the demand to the top coat bed of material is nonsensical, notably, however, when situation is not in this way When, the presence of the top coat bed of material is beneficial.According to an exemplary embodiment, the top coat bed of material includes the material with following characteristic Material: do not turn yellow, gloss retention (for example, the rank for making gloss be maintained at about 80 to about 90 gloss units) and ductility.

In one exemplary embodiment, the top coat bed of material includes polyurethane-based material.Many suitable top coat material are It is commercially available, including for example by the PRC Desoto of California Glenn Dai Er (Glendale, CA) International, Inc. are with trade name DESOTHANE HS (for example, 900 (CA8000/B900A of DESOTHANE HS BAC Or CA8000/B900B)) polyurethane coating sold or Akzo-Nobel by Illinois Wo Jigen (Waukegan, IL) The polyurethane coating (for example, ECLIPSE BAC 900) that Aerospace Coatings is sold with trade name ECLIPSE.

Preferably, the chemical substance of the top coat bed of material is selected to promote the underlayer of itself and paint film applique to bond.According to the reality Apply the one aspect of example, the surface tension of the underlayer of paint film applique about 5 dynes of surface tension of the upper top coat bed of material covered/ In centimetre.According to this embodiment on the other hand, the top coat bed of material includes excessive isocyanate-functional part, the isocyanates Excessive isocyanide in the underlayer (excess isocyanate reactivity portion applies on the underlayer) of functional moiety and paint film applique The reaction of acid esters reactivity part.According to this aspect of the invention, it is formed between the top coat bed of material and the underlayer of paint film applique Covalent bond.This covalent bond usually (for example, depending on the key of Van der Waals force, such as is usually glued with pressure-sensitive than other kinds of key Mixture uses relevant key) it is more steady, it is therefore preferred.

Preferably, in order to maximize the gloss retention, soil resistance and other required performance characteristics of paint film applique, top coat The bed of material has relatively high molecular weight.Although that is, according to some embodiments of the present invention can be by being extruded into top Dope layer, but the top coat bed of material preferably has enough molecular weight, so that its extrusion is unrealistic (that is, if it is polyurethane, then Polyurethane is not considered extrusion grade polyurethane by those of ordinary skill in the art).In a preferred embodiment, in addition to this hair Except bright carrier layer, the top coat bed of material is also in-situ polymerization.

In one embodiment, when there are the top coat bed of material, the top coat bed of material with a thickness of about 1 micron to about 28 microns.? In one further embodiment, the top coat bed of material with a thickness of about 5 microns to about 20 microns.In another further embodiment In, the top coat bed of material with a thickness of about 5 microns to about 15 microns.In another further embodiment, the thickness of the top coat bed of material It is about 5 microns to about 12 microns.In another further embodiment, the top coat bed of material it is micro- with a thickness of about 5 microns to about 7 Rice.However, without departing from the spirit and scope of the present invention, the thickness of the top coat bed of material can be with significant changes.

In order to protect the top coat bed of material, when there are the top coat bed of material, polymer linner can be used (for example, transparent polyester serves as a contrast In) etc., and remove the polymer linner before or after by paint film decal application to substrate.

The formation of paint film applique

According to the knowledge of those skilled in the art, forms each individual course of paint film applique and assemble them into multi-layer paint films Applique.However, carrier layer is formed in situ on nonferrous layer when forming carrier layer, the nonferrous layer for generating carrier layer and being supported Layered product, the non-essential adhesive phase of paint film applique can be formed after the time in a main surface of layered product And/or the non-essential top coat bed of material.

In order to prepare adhesive phase, any suitable method can be used.For example, as on a carrier layer directly (for example, It is in situ) alternative solution that forms adhesive phase, according to one embodiment and as it is known to the person skilled in the art, can be by institute The binder film of thickness is needed to be cast on release film.Then, in this embodiment it is possible to the adhesive that will be supported on release film Film and carrier layer assemble, and remove release film before paint film applique is adhered to product surface.

Although in addition not limiting in terms of assemble method and sequence, at least carrier layer is in-situ polymerization.According to this The further aspect of embodiment prepares each layer in other individual courses of paint film applique before being assembled into paint film applique. As known in the art, any suitable method can be used to form each layer in other individual courses.

In order to prepare the non-essential top coat bed of material, any suitable method can be used.For example, simultaneously according to one embodiment And as it is known to the person skilled in the art, the film comprising the top coat bed of material with required thickness can be cast to smooth film (example Such as polyester film) on to form the supported top coat bed of material.In one embodiment, the top coat bed of material supported is then assembled into packet Include on the side that the layered product of at least one carrier layer and at least one nonferrous layer exposes outward-that is, any with being assembled with above The main surface of the opposite layered product of the main surface of non-essential adhesive phase.The smooth film for being used to form the top coat bed of material can be retained in In component, until by paint film decal application to product surface, to provide additional protection during the transport and storage of thin slice. According to this embodiment, any suitable method can be used to assemble the top coat bed of material and layered product.According to another embodiment, root The top coat bed of material is formed by the way that the top coat bed of material to be applied directly on layered product according to conventional method.

Although above-mentioned processing needs to form individual course and then these layers is bonded together to form paint film applique, root According to another embodiment of the invention, some paint film decal layers can be formed simultaneously, for example, by with the liquid of polymerisable compound Body form starts the coextrusion of polymerisable compound, the step usually below about 40 DEG C at a temperature of carry out-for example, at one It is carried out at about room temperatures in embodiment.Other than carrier layer, layer other than carrier layer can with in-situ polymerization film form, such as Described in the United States Patent (USP) of Patent No. 8,828,303 and the U.S. Patent Publication of Publication No. US-2011-0137006-A1. No matter which kind of method is used, which can be continuous processing or batch processing.

Paint film applique purposes

Paint film applique of the invention can be used for such as transport, the series of indoor of building and sport-goods trade and outdoor and answer With.Paint film applique can advantageously apply in at least part on the surface of the product of any required paint.In addition to many other Using these products further include such as motor vehicles (for example, automobile and aircraft) and non power driven vehicle (for example, tradition is voluntarily Vehicle).The surface for applying paint film applique can otherwise paint or not paint.

Although paint film applique of the invention can have the textured surface of exposure outward when being applied in underlay substrate, But paint film applique of the invention preferably has smooth surface and on the whole substantially uniform thickness, to provide their surfaces The ability of required aesthetic characteristic maximizes.

In use process, by paint film decal application to surface, preferably in a manner of meeting as surface shape.Especially When coated film decal application is when non-planar surfaces, restorability is important and preferred.If paint film applique cannot be well Restore, then may occur micro-crack when applique is pulled too far.Embossment may be needed to cut (relief in this case Cut), so as to by this paint film decal application in substrate, especially with the complex surface with convex surface and concave character substrate. However, preferred embodiment in accordance with the present invention, when complex surface, does not need embossment and cuts when by paint film decal application of the invention It cuts.This paint film applique can adapt to easily because of its restorability.

Knowledge based on those skilled in the art, paint film applique of the invention can be applied to product easily and successfully Surface.Generally removing it, existing any release lining is viscous after adhesive to expose above for adhesive phase (if present) It closes using the surface for having paint film applique.When using pressure sensitive adhesive layer, paint film applique can be glued fast to surface It more successfully relocates before.

Embodiment

Exemplary test method

Exemplary embodiment of the present invention and application are described in conjunction with following test method.

Fissipation factor test method

Use the trade name TA Instruments that can be obtained from TA Instruments (Delaware State Newcastle) The Dynamic Mechanical Analyzer of DMA Q800 carries out the test with tension mode.The use of length is 5-12mm, width be 4-8mm and With a thickness of the nominal sample size of 0.02-0.2mm.Use the frequency of 1Hz, 0.3% strain and 3 DEG C/min of heating rate Carry out measured value to determine the fissipation factor of sample.

Storage modulus test method

Use the trade name TA Instruments DMA Q800 of TA Instruments (Delaware State Newcastle) Dynamic Mechanical Analyzer the test is carried out with tension mode.The use of length is 5-12mm, width be 4-8mm and with a thickness of The nominal sample size of 0.02-0.2mm.Using the frequency of 1Hz, 0.3% tension and 3 DEG C/min of heating rate are measured Value is to determine the storage modulus of sample.

Solvent resistance test method

The roundel (diameter 25mm × 0.16mm is thick) of every kind of material is immersed in individual tank, contains 16mL in each tank Tetrahydrofuran (THF).The dissolution and/or swelling of the disk in each embodiment are assessed after five minutes.In order to assess each sample, If disk is no longer completely, the content in tank to be made to pass through 200 mesh stainless steel filters.If without cutting on sieve Solid or gel residue are stayed, then confirms that disc material has been completely dissolved and not has simply been broken into fine debris.If Disk was still completely, then to remain immersed in disk in THF 6 hours in total at 5 minutes.After total co-impregnation 6 hours, Will disk removed from tank and measure its diameter immediately.Hereafter, disk is air-dried.About after twenty four hours, measure again The diameter of disk.

Comparing embodiment C1

It is assessed according to above-mentioned solvent resistance test method from Argotec, LLC (Greenfield, Massachusetts (Greenfield, MA)) commercially available from 49510 thermoplastic polyurethane film disk of ARGOTEC.After five minutes, disk is no longer complete , it was demonstrated that it has been completely dissolved.

Comparing embodiment C2

It is assessed according to above-mentioned solvent resistance test method from Argotec, LLC (Greenfield, Massachusetts (Greenfield, MA)) commercially available from 46510 thermoplastic polyurethane film disk of ARGOTEC.After five minutes, disk is no longer complete , it was demonstrated that it has been completely dissolved.

Embodiment 1

The film 3 prepared according to following exemplary preparation (referring to table 2 and 5) is assessed according to above-mentioned solvent resistance test method Disk.After impregnating 6 hours, the diameter for measuring disk is the 160% of its original size.After air-drying, it is original that disk is restored to its 25 mm dias, it was confirmed that the evaporation of THF.

Exemplary formulation

The method according to described in the United States Patent (USP) of Patent No. 8,828,303 and described below each layer can be used Component prepares flawless polymer film and the paint film applique comprising the polymer film.

Component

Table 2

Carrier layer

Based on proportional quantities shown in component described in table 2 and table 3-5, is formed and be used for the three of paint film applique of the invention A different carrier layer.Report accounts for the weight percent of the total weight of the resulting film including carrier layer.Component described in table 2 The in-situ polymerization on nonferrous layer (being described as follows).

Table 3 (film 1)

Weight %	Component
		53.0319	High molecular weight polyols
29.0160	Middle-molecular-weihydroxyethyl polyalcohol A
		0.5223	Low molecular weight polyols
0.0049	Catalyst
		0.9852	UV initiator
0.4926	UV stabilizer
		10.9471	Isocyanates

Table 4 (film 2)

Table 5 (film 3)

Weight %	Component
		10.5903	Middle-molecular-weihydroxyethyl polyalcohol B
22.5044	Middle-molecular-weihydroxyethyl polyalcohol D
		10.4844	Low molecular weight polyols
0.0049	Catalyst
		0.9852	UV initiator
0.4926	UV stabilizer
		54.9382	Isocyanates

Nonferrous layer

By the poly- ammonia of solvent type that will be purchased from the trade name ECA-518 of Columbus, Ohio city entrochem, inc. The color concentrate of ester paint and the trade name ECA-505 purchased from Columbus, Ohio city entrochem, inc. mixes, Form nonferrous layer.Blend is coated so that dry thickness is about 10 microns to about 100 microns.

The top coat bed of material

The acrylic polyurethane top coat bed of material for paint film applique of the invention is by aliphatic acrylic polyalcohol and rouge Fat race polyisocyanic acid ester polymer is formed, these components in-situ polymerization on a carrier layer after being applied as about 10 microns of thickness.

Adhesive phase

Adhesive phase for paint film applique of the invention is formed based on adhesive component described in table 2, and is located at It is opposite with nonferrous layer in carrier layer.

It is of the invention various to repair in the case where not departing from by spirit and scope defined in the appended claims of the invention Change and variation is apparent to those skilled in the art.It should be noted that described in following any claim to a method Step is not necessarily required to execute according to their sequence of enumerating.Those of ordinary skill in the art will recognize from their sequence of enumerating To the variation for executing step.

Any theory as described herein can all be subjected to waiting the variation further tested and analyzed.Therefore, inventor does not beat It calculates by for example, to facilitate and paint film applique and each layer of this paper provided in conjunction with the physical qualitative factor described therein The constraint of any theory.

Claims (25)

1. a kind of paint film applique comprising:

It is non-essential, the top coat bed of material；

The carrier layer of in-situ polymerization；

Nonferrous layer；And

It is non-essential, adhesive phase.

2. paint film applique according to claim 1, which is characterized in that the paint film applique is opaque.

3. paint film applique according to claim 1, which is characterized in that the nonferrous layer includes pigment.

4. paint film applique according to claim 1, which is characterized in that the nonferrous layer is in-situ polymerization.

5. paint film applique according to claim 1, which is characterized in that the carrier layer is flawless.

6. paint film applique according to claim 1, which is characterized in that the carrier layer is based on polyurethane.

7. paint film applique according to claim 1, which is characterized in that the carrier layer of the in-situ polymerization is not substantially free of The solvent of reaction.

8. paint film applique according to claim 1, which is characterized in that the paint film applique successively includes the top coat material Layer, the carrier layer of the in-situ polymerization, the nonferrous layer and described adhesive layer.

9. paint film applique according to claim 1, which is characterized in that the paint film applique successively includes the top coat material Layer, the nonferrous layer, the carrier layer of the in-situ polymerization and described adhesive layer.

10. paint film applique according to claim 1, which is characterized in that the carrier layer of the in-situ polymerization with it is described coloured Layer is the same and coloured.

11. paint film applique according to claim 1, which is characterized in that including the top coat bed of material.

12. paint film applique according to claim 11, which is characterized in that the top coat bed of material is based on polyurethane.

13. paint film applique according to claim 1, which is characterized in that when according to fissipation factor test side as described herein When method is tested the carrier layer of the in-situ polymerization as independent film, the peak loss of the carrier layer of the in-situ polymerization because Son is at least about 0.5.

14. paint paint film applique according to claim 1, which is characterized in that tested when according to fissipation factor as described herein When method is tested the carrier layer of the in-situ polymerization as independent film, the peak loss of the carrier layer of the in-situ polymerization The factor about occurs at least about 35 DEG C of temperature.

15. paint film applique according to claim 1, which is characterized in that when according to fissipation factor test side as described herein When method is tested the carrier layer of the in-situ polymerization as independent film, the high loss of the half of the carrier layer of the in-situ polymerization because Son occurs in the temperature span less than about 40 DEG C.

16. paint film applique according to claim 1, which is characterized in that described adhesive layer exists and includes pressure-sensitive adhesion Agent.

17. paint film applique according to claim 16, which is characterized in that further include on the outer surface of described adhesive layer Release film.

18. paint film applique according to claim 1, which is characterized in that it is micro- that the overall thickness of the paint film applique is less than about 130 Rice is thick.

19. a kind of product comprising at least one surface, the surface have at least a portion described in claim 1 Paint film applique.

20. product according to claim 19, which is characterized in that the product includes motor vehicles.

21. it is a kind of using paint film applique described in claim 1 come the method to the finish coatings on motor vehicles, the method Include:

The paint film applique of claim 1 is provided；With

Thin slice is applied to the surface of the motor vehicles.

22. a kind of method for forming paint film applique according to claim 1, which is characterized in that at least described in-situ polymerization Carrier layer and nonferrous layer by be coextruded in-situ polymerization polymerisable compound to be formed simultaneously this at least two layers formation.

23. a kind of method for forming paint film applique according to claim 1, which is characterized in that the nonferrous layer is solvent It casts.

24. a kind of method for forming paint film applique according to claim 1, which is characterized in that the nonferrous layer is by organic Solvent cast forms.

25. a kind of method for forming paint film applique according to claim 1, which is characterized in that the nonferrous layer is by water-soluble Liquid is cast.